Cu⁰/TiO₂ Nanoparticles as Active Catalyst for H₂ Production from Dimethylamine Borane

Abstract

The study reports the preparation and characterization of low cost Cu 0 nanoparticles obtained from reduction of impregnated Cu 2 + ions on the surface of titanium(IV) oxide (TiO 2 ) during hydrogen releasing from dimethylamine borane (DMAB). Cu 0 / TiO 2 nanoparticles act as active catalyst with a turnover frequency 59.9 h À 1 in H 2 releasing of dimethylamine borane at 60.0 � 0.5°C. The obtained catalysts, Cu 0 /TiO 2 NPs, were isolated from reaction medium and characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), Ultravioletvisible spectroscopy (UV vis.) and X-ray photoelectron spectro-scopy (XPS) techniques. Cu 0 /TiO 2 nanoparticles with different metal loadings (4.0-8.0 % Cu wt.) were prepared and tested as catalyst in dehydrogenation of dimethylamine borane at 60.0 � 0.5°C. All results reveal that Cu 0 NPs dispersed on the surface of titania were found as 2.96 � 0.83 nm. The highest catalytic activity was achieved for Cu 0 /TiO 2 NPs, 0.6 % Cu wt. with a turnover frequency 59.9 h À 1 in H 2 releasing of dimethylamine borane at 60.0 � 0.5°C. The work reported here also includes the kinetic study depending on the temperature.

Polymer Hydrogel Supported Ni/Pd Alloys for Hydrogen Gas Production from Hydrolysis of Dimethylamine Borane with a Long Recyclable Lifetime

“…As far as we know, the activation energy in the present study represents the lowest in a hydrolysis reaction of DMAB so far. Besides, compared with the reactions in the organic phases [ 3 , 4 , 5 , 6 , 7 , 8 , 9 , 10 , 11 , 12 , 13 , 14 , 15 , 16 , 17 , 18 , 19 , 20 , 21 , 22 ] and under solvent-free conditions [ 23 , 24 , 25 ], the activation energy in the aqueous phase is also lower, indicating that the breaking of B–H bonds occurs smoothly with the attack of water.…”

“…DMAB is cheaper and better than NaBH 4 and AB on the market, with the potential to reduce the cost of hydrogen production. At present, most hydrogen production reactions based on DMAB are carried out in organic solvents such as dioxane, tetrahydrofuran, and toluene [ 3 , 4 , 5 , 6 , 7 , 8 , 9 , 10 , 11 , 12 , 13 , 14 , 15 , 16 , 17 , 18 , 19 , 20 , 21 , 22 ] or via solvent-free dehydrogenation of DMAB [ 23 , 24 , 25 ]. However, in terms of green energy and safety, it is of critical importance to replace the organic solvents with water.…”

“On–Off” Control for On-Demand H2 Release upon Dimethylamineborane Hydrolysis over Ru0.8Ni0.2/MoS2 Nanohybrids

“…In the past two decades, H 2 gas is comprehensively deemed as a green, sustainable, environmental-friendly future energy source for displacing fossil fuels, − preventing further environmental deterioration, and meeting ever-increasing global energy demand. − However, the large-scale practical and industrial application of H 2 has been severely limited by its ultra-low density, liquefaction problem, and high transportation costs. − To overcome this difficulty, all kinds of hydrogen storage materials, e.g., HCOOH, − N 2 H 4 , − NaBH 4 , N 2 H 4 BH 3 , − NH 3 BH 3 , − and Me 2 NHBH 3 , have been designed and explored for the safe production, transport, and storage of hydrogen gas. Among them, dimethylamineborane (Me 2 NHBH 3 ) has recently attracted wide attention due to its cost-effectiveness (compared to NH 3 BH 3 ), excellent hydrogen storage capacity, non-flammability, non-toxicity, excellent stability, and solubility in water. − In spite of the fact that remarkable developments have been realized in the design and development of novel nanocatalysts for H 2 evolution from dimethylamineborane hydrolysis in water (eq ), − the development of “on–off” control for on-demand H 2 evolution upon dimethylamineborane hydrolysis is still a matter of supreme importance, however. − Herein, we synthesized a string of MoS 2 nanosheet-supported RuNi nanohybrids (Ru x Ni 1– x /MoS 2 ), by fixation of RuNi nanoparticles at the MoS 2 surface, for H 2 evolution upon dimethylamineborane hydrolysis at 30 °C. Particularly, the thin MoS 2 nanosheet was widely applied in photocatalytic H 2 production, antibacterial agents, microwave absorption, and water treatment due to its unique optical, physicochemical, and electrical properties. − These bimetallic Ru x Ni 1– x /MoS 2 exhibited higher ca...…”

Green Approaches to Dehydrogenation of DMAB Catalyzed by Starch Stabilized Ru(0), Cu(0) and Ni(0) Nanoparticles in the Absence of a Solvent

“…Although the production, storage and use of hydrogen, which is a promising energy carrier, is still an important problem for industrial applications, all the researches to solve this problem are focused on to obtain alternative amine borane derivatives to be used as solid storage materials with thermal stability, ease of hydrogen release and high hydrogen density. For this purpose, many studies are carried out with commonly used solid hydrogen storage materials such as ammonia borane [32,33] and dimethylamine borane, [34,35] as well as new derivatives such as ethylene diamine-bisborane, [36][37][38] methylamine borane [39][40][41] and morpholine borane. [42,43] Among them, dimethylamine-borane (Me 2 NHBH 3 , DMAB), which has many properties such as low melting point, high stability, durability, sustainable environmental and economic advantages, is one of the most preferred amine borane derivatives in hydrogen production.…”